TWI343406B - Halide anions for metal removal rate control - Google Patents

Description

1343406 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a polishing composition and a method of polishing a substrate using the polishing composition. [Prior Art] Compositions, systems, and methods for planarizing or polishing a surface of a substrate, particularly for chemical mechanical polishing (CMP), are well known in the art. The polishing composition (also referred to as a polishing slurry) typically contains an abrasive material in an aqueous solution and is applied to the surface by contacting the surface with a polishing pad impregnated with the polishing composition, when used to polish a substrate comprising a metal, Polishing compositions often comprise an oxidizing agent. The purpose of the oxidant is to transform the surface of the metal into a material that is softer and more abrasive than metal. Therefore, polishing compositions comprising an oxidizing agent together with an abrasive generally require less aggressive grinding of the substrate, which reduces mechanical damage to the substrate caused by the grinding process. In addition, the presence of oxidants often increases the rate of metal removal and increases the yield in production equipment. The development of next-generation semiconductor devices emphasizes the use of metals with lower resistivity values than previous generation metals such as 'Ming' (such as copper). ) to reduce the capacitance between the conductive layers on the device and increase the frequency at which the circuit can operate. One way to fabricate flat copper circuit traces on a oxidized substrate is referred to as an inlay process. According to this process, the ceria dielectric surface is patterned by a conventional dry etching process to form holes and shoulders 1 for vertical and horizontal interconnection. The patterned surface is coated with an adhesion promoting layer such as tantalum or titanium, and/or a diffusion barrier layer such as nitride or titanium nitride. The adhesion promoting layer and/or the H9564.doc 1343406 diffusion barrier layer is subsequently coated with a copper layer. Chemical mechanical polishing is used to reduce the thickness of the outer layer of copper and the thickness of any adhesion promoting layer and/or diffusion barrier layer until a flat surface is exposed which exposes the elevated portion of the surface of the dioxide. The channels and trenches are still filled with conductive copper that forms a circuit interconnect. Polishing of substrates comprising tantalum and copper layers typically requires the addition of a conventional copper inhibitor such as benzotriazole (BTA) or methyl-cracked triazole (ηι·ΒΤΑ) to the polishing slurry to limit copper. The rate of removal of the layer. Polishing of the button layer typically requires an oxidizing agent to achieve a useful removal rate, such as a peroxide (e.g., hydrogen peroxide) or potassium iodate. The tantalum layer is typically polished at a high pH value. Even for slurries having a low pH value and containing an oxidizing agent such as hydrogen peroxide or potassium iodonium, the steel removal rate is still high. In addition, the oversize is a strong oxidizing agent which can be combined with the polishing composition. Other component reactions 'This limits the stability of the polishing composition and thus limits its effective pot life. For example, η, hydrogen peroxide degrades the ruthenium except by etching the copper wire on the surface of the substrate by chemical etching. And the substrate of copper still need an alternative polishing system and polishing method. [Invention] The present invention provides a chemical mechanical polishing system for polishing a substrate. The system comprises: (a) a polishing assembly, Selecting a group consisting of a polishing pad, an abrasive, and combinations thereof; (b) a liquid carrier; (c) an oxidizing agent that oxidizes at least a portion of _$• its ic ^, an earth plate where the amount of the oxidant is present The liquid carrier and the weight of any component dissolved or 'floating in it' are 0.5% by weight or less; and (4) the elemental anion' is selected from the group consisting of vapor, bromide and combinations thereof, 119564.doc 1343406 A group of liquid carriers in which any component is dissolved or suspended has a pH of 3 or less. The present invention also provides a method of chemical mechanical polishing of a substrate comprising: (1) substrate and a chemical mechanical polishing system In contact, the chemical mechanical polishing system comprises: (a) a polishing assembly selected from the group consisting of polishing pads, abrasives, and combinations thereof, (b) a liquid carrier, (c) an oxidant, which oxidizes at least a portion a substrate, wherein the oxidizing agent is present in an amount of 5% by weight or less based on the weight of the liquid carrier and any component of the solution or suspension thereof, and (d) a dentate anion selected from the group consisting of a vapor, Bromide and its a group consisting of a composition in which a liquid carrier in which any component is dissolved or suspended has a pH of 3 or less; (π) moving the polishing assembly relative to the substrate; and (iii) polishing at least a portion of the substrate to polish The substrate, wherein the liquid carrier in which any of the components are dissolved or suspended has a pH of 3 or less. [Embodiment] The present invention provides a chemical mechanical polishing system for polishing a substrate, the system comprising the following The following components consist essentially of or consist essentially of: (a) a polishing assembly selected from the group consisting of polishing pads, abrasives, and combinations thereof; (b) a liquid carrier; (c) an oxidizing agent, And oxidizing at least a portion of the substrate, wherein the oxidizing agent is present in an amount of 5% by weight or less based on the weight of the liquid carrier and any component dissolved or suspended therein; and (d) a sulphide anion selected A group of free vapor bromides and combinations thereof that have a liquid carrier in which any component is dissolved or suspended has a pH of 3 or less. The liquid carrier, oxidizing agent, halogen anion, and any other component (e.g., abrasive) dissolved or suspended in the liquid carrier t constitute a polishing composition H9564.doc 1343406. The components described herein are based on the total weight of the polishing composition unless otherwise specified. The substrate to be polished may be any drop. Human, J mouth substrate. Suitable substrates include, but are not limited to, integrated circuits, memory or hard 榉, 厶 a B 哚, metal, interlayer dielectric (Ild) devices, semiconductors, MEMS components, ferroelectrics and magnetic heads . The substrate may comprise a metal layer. The metal layer can comprise any suitable metal. For example, the metal layer may comprise copper, tantalum (e.g., nitride button), titanium, aluminum, nickel, platinum, rhodium, ruthenium or iridium. The substrate may further comprise at least one other layer, such as an insulating layer. The insulating layer can be a metal oxide, a porous metal oxide, glass, an organic polymer, a fluorinated organic polymer, or any other suitable high or low insulating layer. The metal layer can be placed on another layer. More preferably, the substrate has at least one layer of germanium and at least one layer of copper. The polishing assembly can comprise, consist of, or consist essentially of a polishing pad (e.g., a polishing surface). The polishing pad can be any suitable polishing pad, many of which are known in the art. Suitable polishing pads include, for example, woven or non-woven polishing pads. In addition, suitable polishing pads can comprise any suitable polymer having varying density, hardness, thickness, compressibility, compression resilience, and compression modulus. Suitable polymers include, for example, polyethylene bake, polyvinyl fluoride, nylon, fluorocarbon, polycarbonate, poly, polyacrylate, polyether, polyethylene, polyamine, polyurethane Ester, polystyrene, polypropylene, coformecl products, and mixtures thereof. The polishing pad can comprise fixed abrasive particles' or polishing pads on or in the polishing surface of the polishing pad that can be substantially free of fixed abrasive particles. The fixed abrasive polishing pad comprises a lining having abrasive particles adhered to the polishing surface of the polishing pad by an adhesive, a binder, a ceramic polymer, a resin or the like by U9564.doc 1343406; or, grinding The agent, which has been injected into the polishing pad, is integral with the polishing pad, such as a fiber batt infused with an abrasive-containing polyurethane dispersion. Fixing the polishing pad eliminates the need to provide a polishing component in the polishing composition.

The polishing pad can have any suitable configuration. For example, the polishing pad can be circular and, in use, typically has a rotational motion about an axis that is perpendicular to the plane defined by the surface of the pad. The polishing pad can be cylindrical with its surface acting as a polishing surface'and' typically has a rotational motion about the central axis of the cylinder when in use. The polishing pad can take the form of an endless belt that typically has a linear motion relative to the edge of the cut being cut. The polishing pad can have any white y-like shape and, when in use, has a reciprocating or swiveling motion along a plane or a half circle. Many other variations are readily suggested by those skilled in the art. The polishing assembly may comprise an abrasive, and the abrasive may be fixed to the polishing pad or

Can be suspended in a liquid carrier (eg, water). The abrasive can be in any suitable form (e.g., abrasive particles). Abrasives are typically in particulate form and are suspended in a liquid carrier (e.g., water). The abrasive can be any suitable abrasive. For example, the abrasive can be natural or synthetic and can comprise, consist essentially of, or consist of: a metal oxide, a carbide, a nitride, a silicon carbide, or the like. The abrasive can also be polymeric particles or coated particles. The abrasive typically comprises metal oxide particles. Preferably, the abrasive is a metal oxide selected from the group consisting of alumina, cerium oxide, cerium oxide, oxidative error, coformed products thereof, and combinations thereof. The abrasive particles typically have an average particle size of 2 〇 nml 5 〇〇 η Π 9564.doc (e.g., 'average particle diameter). Preferably, the abrasive particles have an average particle size of from 2 Å to 3 Å (e.g., < 70 nm to 300 nm or 1 〇〇 nn ^ 200 nm). Any suitable amount of abrasive can be present in the polishing composition. Generally, 研磨.01% by weight or more (e.g., 0_05% by weight or more) of the abrasive will be present in the polishing composition. More typically, 1% by weight or more of the abrasive will be present in the polishing composition. The amount of the abrasive in the polishing composition is usually not more than 20% by weight 'more usually, not more than 15% (e.g., not more than 10% by weight). Preferably, the amount of the abrasive in the polishing composition is from 重置1 to 10% by weight, and more preferably 5% by weight or less. The use of this low concentration of abrasive significantly reduces the cost of manufacturing the polishing composition and reduces the likelihood of scratching or otherwise producing a defective substrate. The liquid carrier is used to facilitate application of the abrasive (when present and suspended in the liquid carrier) to the surface of a suitable substrate to be polished (e.g., to be planarized), an oxidizing agent, a dentate anion, and any optional additives. The liquid carrier can be any suitable solvent 'including lower alcohols (e.g., methanol, ethanol, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), water, and mixtures thereof. Preferably, the liquid carrier comprises water, consists essentially of or consists of water, more preferably deionized water. The oxidizing agent can be any suitable oxidizing agent. Preferably, the oxidizing agent is selected from the group consisting of: bromate 'bromide, gas salt, gas sulfite, hydrogen peroxide, hypogaslate, iodate, monoperoxy Sulfate, monoperoxy sulfinium salt, monoperoxyphosphate, monoperoxy-low-phosphonium salt (m〇n〇per〇xyhyp〇ph〇sphate), monoperoxy pyrophosphate, organic Organo-halo-〇xy compound, perrhenate, high-acid 119564.doc. More preferably, the oxidizing agent is nitrogen peroxide, potassium citrate or a combination thereof. The wood oxidizing agent is present in the polishing composition in an amount of 5% by weight or less. The polishing composition comprises 〇.丨% by weight or more (e.g., 〇 2% by weight of 5 eve) oxidizing agent. The polishing composition preferably comprises 0.45% by weight or less of 〇4% by weight or less, or 3% by weight or less of the oxidizing agent. More preferably, the oxidizing agent is present in the polishing composition in an amount of 2% by weight or less. Unexpectedly, the relatively low concentration of oxidant was used to successfully reduce the copper removal rate exhibited by the polishing system with a reduced rate of enthalpy removal. Halogen anions can be produced from any source. Preferably, the source is selected from the group consisting of acid vapors or bromides, metal oxides or bromides, Group III A vapors or bromides, vapors or bromide ammonium salts or bond salts. , transition metal vapors or bromides and combinations thereof. More preferably, the source is selected from the group consisting of gasification hydrogen, magnesium gasification, calcium chloride, gasification hydrazine, gasification hydrazine, gasification potassium, gasification hydrazine, gasification lithium, gasification sodium, Gasified hydrazine, tetrabutylammonium vapor, tetramethylammonium hydride, tetraethyl gasification bond, tetrapropylammonium hydride, alkylbenzyldimethylammonium chloride (wherein alkyl is Cl-C2) 〇alkyl), aluminum chloride, gallium chloride, indium sulfide, gasification hydrazine, zinc hydride, vaporized copper, gasified iron, gasified ferrous iron, tetrabutyl desertification, tetradecyl bromination Ammonium, tetraethylammonium bromide, tetrapropylammonium bromide, alkylbenzyl dimethyl evolution (wherein the alkyl group is C 1 - C 2 Q sulki), desertification hydrogen, desertification, desertification lithium , potassium bromide, barium bromide, sodium bromide, magnesium bromide, calcium bromide, barium bromide, barium bromide, aluminum bromide, gallium bromide, indium bromide, barium bromide, desertification I19564.doc 1343406 Zinc, copper bromide, iron bromide, ferrous bromide and combinations thereof. The alkane anion can have any suitable concentration in the polishing composition wipe. Typically, the concentration of the anion anion in the polishing composition is from 〇5 mM to 5 壤. The concentration of the dentate anion in the polishing composition is preferably 7 sec or less, more preferably 2 mM or less (for example, e.g. or less or "Μ or less". Concentration of _ anion in the polishing composition. It is preferably 秘1 secret or larger, and more preferably 0.2 mM or more (for example, 〇3 乂 or greater or 0.4 mM or more).

The liquid carrier having any of the components dissolved or suspended therein may have any suitable pH. The actual positive value of the polishing composition will depend, in part, on the type of substrate to be polished. The polishing composition has a value of 3 or less (eg, 2.2 or less 'or 2 or less). Typically, the polishing composition has 丨 or greater (eg, '1 to 3, 1 to 2_2, or 1 to 2 ) PH value.

The pH of the polishing composition can be achieved and/or maintained by any suitable means. More specifically, the polishing composition may further comprise a pH adjuster, a pH buffer, or a combination thereof. The pH adjusting agent can be any suitable positive value adjusting compound. For example, the pH adjusting agent can be any suitable acid, such as an inorganic acid, an organic acid, or a combination thereof. By way of example, the acid can be nitric acid. The pH buffering agent can be any suitable buffering agent, for example, a sulphate, an acetate, a borate, a sulfonate, a carboxylate, an ammonium salt, & analogs thereof. The polishing composition can comprise any suitable amount of pH adjusting agent and/or positive buffering agent' limiting conditions sufficient to achieve and/or maintain the desired pH of the polishing composition, for example, as described herein. The positive value inside. More preferably, the above-described elemental anion source can be used to adjust and/or maintain the pH of the polishing composition 119564.doc -12. and the D material can comprise a corrosion inhibitor (i.e., a film former). The rot silver inhibitor can be any suitable rot.) The rotted silver contains a hetero atomic official. For example, the corrosion inhibitor J horse has at least one compound of 5 哎 6 Chang, the heterocyclic organic compound of the reactive functional group, and the middle % contains at least one nitrogen atom, for example, salivation is preferred at first. The preparation contains at least one record. More preferably, the rot (iv) preparation is selected from the group consisting of hong triazole, i 2 ^ three. Sitting, benzene (four) saliva, benzoquinone (four) and their mixture:. The amount of the corrosion inhibitor is usually 〇·〇〇〇1% by weight to 3 parts by weight 0.001% 〇/〇 to 2% by weight). The live horse polishing composition can comprise a chelating agent or a complexing agent. The binder is any suitable chemical additive that enhances the removal rate of the removed substrate layer. Suitable f-agents or complexing agents may include, for example, a few base compounds (e.g., ethylpyruvate and analogs thereof), simple carboxylates (e.g., acetates, aryl carboxylates, and the like) a carboxylate containing one or more (iv) groups (for example, acetate, lactate, gluconate, gallic acid and salts thereof, and the like), di-carboxylate, tri-carboxyguanidinium salt and polycarboxylic acid Salt (eg, oxalate, terephthalate, citrate, succinate, tartrate, malate, ethylenediaminetetraacetate (eg, EDTA dipotassium), mixtures thereof, and the like) a carboxylate containing one or more sulfonic acid groups and/or phosphonic acid groups, and the like. Suitable chelating or blocking agents may also include, for example, glycols, trihydric or polyhydric alcohols (eg, 'ethylene glycol, o-diphenol, benzophenone, acid, and the like) and amines. Compounds (for example, ammonia, amino acids, amine groups 119564.doc • 13·1343406 alcohols, diamines, triamines and polyamines, and the like). The choice of integrator or combination of agents will depend on the type of substrate layer being removed. It will be appreciated that many of the above compounds may be present as a salt (e.g., metal male, ammonium or analog thereof), in the form of an acid, or as a partial salt. 1. The citrate includes citric acid and its mono-, di- and tri-salts; p- benzene: formate includes p-dicarboxylic acid and its mono-salt (for example, potassium hydrogen benzoate) and Dibasic salts; perchlorates include the corresponding acids (i.e., peroxyacids) and salts thereof. In addition, certain compounds or reagents can perform multiple functions. By way of example, certain compounds may act as chelating agents and oxidizing agents (e.g., certain schizophrenia analogs). The polishing composition optionally includes - or a plurality of other additives. Such additives include - or a plurality of acrylic acid acrylic vinegars (e.g., ethyl acetoacetate and styrene acetoacetate) with polymers, copolymers, oligomers and salts thereof. The polishing composition can comprise a surfactant and/or a rheology control agent, including a viscosity enhancer and a coagulant (e.g., a polymeric rheology control agent such as an amine-methyl polymer). Suitable surfactants can include, for example, cationic surfactants, anionic surfactants, nonionic surfactants, surfactants, mixtures thereof, and the like. Preferably, the polishing composition comprises a nonionic surfactant. An example of a suitable nonionic surfactant is an amount of surfactant in the ethylamine polyoxyethylene interfacially active polishing composition, which is from MGG 1% by weight to 1 weight, preferably 0.0 (H% by weight to 0.1% by weight, 0 $ and more preferably 0.005 wt% to 〇05 wt. /〇). The polishing group will be private 7 Α λ . I 3 defoamer. The antifoaming agent can be any suitable defoaming agent. I19564.doc 1343406 Agent sigma suitable shoulders/packages include, but are not limited to, antimony-based and acetylene glycol-based defoamers. The amount of antifoaming agent in the polishing composition is usually from ι 〇 to (10) ppm.

The gamma of the phosphor group is preferably colloidally stable. The term gum system refers to the liquid of the granules in the liquid carrier. Colloidal stability means always-straightening to maintain the suspension, * seeing the following opening > s forbearing the polishing composition is colloidally stable: when the polishing composition is placed in a (10) ml graduated cylinder and allowed to stand for two hours The particle concentration of the bottom 50 of the cylinder ([B] in g/ml) and the particle concentration in the top 5 of the cylinder ([τ] ' in g/ The difference between ml) divided by the initial 2 particle concentration in the polishing composition ([c], in g/ml) is less than or equal to 〇5 (ie, {[b]_ m}/[C ]S0_5). Preferably, the value of [BHT]/[C] is less than or equal to 〇 3, preferably

The polishing composition can comprise a biocide. The biocide can be any suitable "biological agent such as a "selling saliva" biocide. Biocide in a polishing composition! Typically from 1 to 50 ppm, preferably from 10 to 20 ppm. (U, more preferably small H is equal to QG5, and is preferably less than or equal to 0.01. The polishing composition can be prepared by any suitable technique, and many of these techniques are well known to those skilled in the art. Polishing compositions can be used in batch or continuous processes. Preparation. In general, polishing compositions can be prepared by combining the components in any order. The term "component" as used herein includes individual ingredients (eg, oxidizing agents, abrasives, etc.) and any combination of ingredients ( For example, a liquid carrier, a halogen anion, a surfactant, etc.) The polishing composition can be supplied as a single encapsulation system comprising an oxidizing agent, a dentate anion, a liquid loading 119564.doc 15 and, where appropriate, a grinding shovel. The oxidizing agent may be supplied to the first volume in a dry form or as a solution or dispersion in a liquid carrier, and the acne anion, the liquid carrier and, optionally, the abrasive The V-force agent can be supplied to the second container. The use of a stable oxidizing agent (potassium) allows the oxidizing agent to be supplied to the other group of wounded wipes having the polishing composition because it is less likely to react with other components. The route can substantially reduce the cost of preparing and utilizing the polishing composition. ★ The optional component of the abrasive crucible can be placed in the first or third container or in the second container in a dry form or as a solution in a liquid carrier. In addition, it is suitable that the components in the first or second container have different pH values or have substantially similar or even equal pH values. If the optional component is a solid, it may be in a dry form or as a Available as a ready-to-use in the liquid carrier. The optional components can be supplied separately from the other components of the polishing system and can be, for example, performed by the end user prior to use* for a longer period of time with the other components of the polishing composition. , and σ (for example, before or after the use of the previous week or less, before the use of 1 day or less, before the use of 1 hour or less, before the use of 1 minute or less, or use Before i points Other double containers or combinations of three or more containers of the components of the polishing composition are within the purview of those of ordinary skill in the art. The polishing composition can also be provided as a concentrate. The concentrate should be diluted with an appropriate amount of liquid carrier prior to use. In this embodiment, the polishing composition concentrate may comprise a suitable amount of an oxidizing agent, a dentate anion, and a liquid carrier such that a suitable amount of liquid carrier is used. When diluting the concentrate, each component will be present in the 119564.doc • 16- polishing composition in an amount that is within the appropriate ranges recited above for each component. For example, the oxidizing agent can each be It is believed that the concentration described above for each of the components of the polishing composition is 2 times (eg, '3 times 4 times or 5 times greater) in the concentrate, such that when a suitable liquid carrier is used ( For example, when diluting the concentrate with 2 equivalents of a liquid carrier, 3 parts of an equivalent amount of a liquid carrier, or 4 parts of an equivalent amount of a liquid carrier, respectively, each component will be stated as stated above for each component. The amount in the range exists in the polishing group In the compound. Moreover, as is generally understood by those skilled in the art, the concentrate may contain a suitable portion of the liquid carrier present in the final polishing composition to at least partially protect the oxidizing agent, dentate anion, and other suitable additives such as abrasives. Or all dissolved or suspended in the concentrate. The invention also provides a method of chemical mechanical polishing of a substrate. The method comprises: (i) contacting a substrate with a chemical mechanical polishing system as described herein, (ii) moving the polishing assembly relative to the substrate, and grinding at least a portion of the substrate to polish the substrate. The substrate polishing method of the present invention is particularly suitable for use in combination with a chemical mechanical polishing (CMP) device. Typically, the apparatus comprises: a platen that is in motion and has a velocity resulting from a rotary, linear or circular motion in use; a polishing pad that is in contact with the platen and that moves with the platen during movement; a carrier that holds the substrate to be polished by contact and movement relative to the surface of the polishing pad. Polishing of the substrate occurs by contacting the substrate with the polishing pad and the chemical mechanical polishing composition of the present invention, pulling and moving the polishing pad relative to the substrate, thereby polishing at least a portion of the substrate to polish the substrate. It is expected that the CPM device further includes an in-situ polished endpoint detection system' many 119564.doc -17-1343406 such systems are known in the art. Techniques for verifying and monitoring the polishing process by analyzing light or other radiation reflected from the surface of the workpiece are known in the art. For example, in U.S. Patent No. 5,196,353, U.S. Patent No. 5,433,65, U.S. Patent No. 5,6Q9,5n, U.S. Patent No. 5,643, U.S. Patent No. 5,658,183, U.S. Patent No. 5,73,642, U.S. Patent No. 5 Such methods are described in U.S. Patent No. 5,872,633, U.S. Patent 5,893,796, U.S. Patent 5,949,927, and U.S. Patent 5,964,643. Polishing refers to removing at least a portion of the surface to polish the surface. Polishing may be performed by removing round chisels, pits, dimples, and the like to provide a surface having a reduced surface roughness, but polishing may be performed to introduce or restore surface geometry characterized by intersection of planar segments. shape. For example, where two surfaces intersect to define an edge, polishing the surface by grinding at least a portion of at least one of the surfaces causes the geometry of the edge to change. In embodiments where the or the surfaces define edges for use in a cutting operation (e.g., in polishing of a cutting tool), polishing of the surface can result in re-defining or re-sharpening the edges. As mentioned previously, the substrate preferably has at least one layer of tantalum and at least one layer of steel. It is desirable that the copper layer be removed from the substrate at a rate of 1000 A/min or less (e.g., 8 Å A/min or less, 500 A/min or less, or 300 A/min or less). Unexpectedly, the presence of dentate anions (such as gas ions or > odor ions) effectively reduces the copper removal rate and generally does not reduce the rate of ridge removal, which allows polishing of the substrate to occur in a single Not a multi-step process. This is an improvement over the use of conventional copper inhibitors such as BTA or m-BTA, which is relatively ineffective in reducing the copper removal rate. 119564.doc • 1S - 1343406 is relatively ineffective and can be easily The other components of the polishing system, such as hydrogen peroxide, are degraded. Without wishing to be bound by any particular theory, the low solubility of CUCWC may result in preferential gas ions or (iv) being adsorbed at the Cu+ site, thereby preventing continuous copper oxidation by the oxidant. The following examples are presented to illustrate the invention 'but' are not intended to limit the scope of the invention. Example 1 This example illustrates the effect of the presence of gas anions and other matrices on the copper removal rate in a polishing composition containing cerium oxide and an oxidizing agent.

Eight different polishing compositions were evaluated relative to the copper removal rate. Each composition contained water, 0.5% by weight of polycondensed cerium oxide (25 nm in diameter) & 0.2% by weight of 1 <: 103, and adjusted to a pH of 22 (basic composition) with nitric acid. Additional components are added to the base composition to form other compositions. In particular, the other compositions further comprise 3 〇〇 ppm HCl and a pH adjuster, 10 mM BTA, 20 mM BTA, 10 mM m-BTA, 5 mM m-BTA, 800 ppm h3P04 and a regulator, respectively. 5% by weight of KC1 Log A Logitech polisher with a soft Politex pad was used, with each of the compositions polishing a substrate comprising a copper layer. The Logitech polisher was set to have a downward force of 10.3 kPa (1.5 psi), a platen speed of 110 rpm, a carrier speed of 102 rpm, and a composition flow rate of 150 ml/min. The copper removal rate (A/min) of each composition was determined and is shown in the figure! The bar graph depicts the results. II9564.doc -19· 1343406 The copper removal rate of the basal implant is clearly seen from the information returned in Figure 1. The composition of the present invention having a negative, stomatal having 3 gas ions exhibits a copper removal rate which is about 10 times lower than the rate of the base composition. In contrast, a comparative composition having two BTA, m.BTA or h3P〇4 exhibited a higher copper removal rate than the present invention: a composition containing a gas ion. Example 2 This example illustrates the effect of halogen anions on the removal rate of copper and bismuth in a polishing composition containing cerium oxide and an oxidizing agent.

A variety of polishing compositions were evaluated relative to copper and button removal rates. Each of the compositions contained water, 0.5% by weight of polycondensed bismuth telluride (25 nm in diameter) & 〇 2% by weight of 10 〇 3, and adjusted to a pH of 22 (basic composition) with nitric acid. The compositions differ from one another by the presence of varying concentrations of potassium fluoride, potassium hydride, bromine or potassium iodide.

Each of the compositions was used to polish a substrate comprising a copper layer and a button layer using a Logitech polisher having a soft Politex pad. The Logitech polisher was set to have a downward force of 10.3 kPa (1.5 psi), a plate speed of 110 rpm, a carrier speed of 102 rpm, and a composition flow rate of 150 ml/min. A salt solution of KF, KC1, KBr and KI was mixed into the base composition at the indicated concentration by an in-line mixing system built into the Logitech polisher. The copper and bismuth removal rate (A/min) of each composition was determined. Tables 1 and 2 list the salt type, salt concentration and polishing results. 119564.doc -20· Table 1: Copper removal rate (A/min)

Salt concentration 0 ppm 66 ppm 132 ppm 476 ppm 909 ppm KF 3023 2775 2702 2140 1888 KC1 3023 1047 473 302 266 KBr 3023 319 360 274 318 ΚΙ 3023 30390) 1896(2) 1583(3) N/A 1343406 (1) At 110 ppm; (2) at 218 ppm; (3) at 535 ppm Table 2: 钽 removal rate (A/min) Salt concentration 0 ppm 66 ppm 132 ppm 476 ppm 909 ppm KF 315 358 512 410 362 KC1 315 365 459 421 406 KBr 315 341 343 371 370 It is clear from the information listed in Table 1 that the presence of KC1 and KBr reduces the copper removal rate from 3000 A/min at a concentration of 132 ppm. Up to 500 people / minute. In addition, a 600 ppm KBr is required to reduce the copper removal rate to less than 400 A/min. The information listed in Figure 1 also demonstrates that the presence of KF and KI is ineffective in reducing copper removal rates. It is clear from the information listed in Table 2 that the presence of chloride and bromide does not reduce the group removal rate. More specifically, at a concentration of 132 ppm, the presence of KC1 and KBr increased the button removal rate by 46% and 9%, respectively, compared to the base composition. Example 3 This example compares the effect of various compounds on the copper removal rate in a polishing composition containing cerium oxide and an oxidizing agent. A variety of polishing compositions were evaluated relative to the copper removal rate. Each composition 119564.doc -21- 1343406 contains water, 0.5% by weight of polycondensed cerium oxide (25 nm in diameter) and 0.2% by weight of 〇03, and is adjusted to 2.2 with nitric acid. "[Value (basic composition). The compositions differ from each other by the presence of different concentrations of BTA, KBr, NaBr, KC1, CsCl, HCl, tetrabutyl gasification (TBAC1), hydrazine, KN〇3, KAc, K2SO4, K2CO3, or K3PO4. Each of the compositions was used to polish a substrate comprising a copper layer using a Logitech polisher with a soft Politex pad. The Logitech polisher was set to have a downward force of 9.3 kPa (1.35 psi), a platen speed of 110 rpm, a carrier speed of 102 rpm, and a composition flow rate of 1 50 ml/min. The diluted salt solution is mixed into the base composition by an in-line mixing system built into the Logitech polisher. The copper removal rate (A/min) of each composition was determined. Additive types, additive concentrations, and polishing results are listed in Table 3. Table 3: Copper removal rate (A/min) Additive additive concentration 0 mM 0.66 mM 1.32 mM 6.25 mM BTA 4384 5123 5560 5783 KBr 4384 575 629 266 NaBr 4384 350 398 228 KC1 4384 404 356 337 CsCl 4384 411 355 386 HC1 4384 449 398 346 TBAC1 4384 863 (1) 502(2) 411 w KI 4384 3039 1896 2824 KNO3 4384 - 2255 4281 KAc 4384 4752 4967 - K2SO4 4384 3701 4155 3960 K2CO3 4384 2644 2599 - K3PO4 4384 2712 3353 - (1) at 0.58 mM; (2) at 1.13 mM; (3) at 1.64 mM 119564.doc -22- (s) 1343406 It is clear from the data listed in Table 3 that the base composition has A/min of copper. The presence of the removal rate β BTA does not reduce the copper removal rate. The presence of nitric acid, acetonate, carbonium, sulfuric acid and meal anions did not reduce the copper removal rate below the impurity A/min. (d), (4) The presence of ions and gas ions reduces the copper removal rate to less than 1000 A/min. The type of cation is not a significant factor for the copper removal rate. Example 4 This example illustrates the effect of various additives on the copper and group removal rates in a polishing composition comprising yttrium stabilized cerium oxide and ceric acid. Nine different polishing compositions were evaluated relative to copper and button removal rates. Each composition comprises water, 〇5 weight ° / 〇 钸 (IV) stabilized polycondensed cerium oxide (28 nm diameter, 500 ppm Ce (IV)) at a pH of 2.1 ± 0.1 (basic composition) and 0.20% by weight of KIO3 oxidant. The base composition is divided into two batches' these two batches form the composition Α and F. 1,2,4-Trisal (TAZ), CsCl, BTA, Cs2C03, KC1, and combinations thereof were added to the two batches of the base composition as shown in Table 4 to form compositions B-E and G-I. A substrate comprising a copper layer and a button layer was polished using a CETRA polisher with an A110 hard crucible. The CETR polisher was set with a downward force of 10.3 kPa (1.5 psi), a platen speed of 133 rpm, a carrier speed of 120 rpm, and a composition flow rate of 60 ml/min. The copper and bismuth removal rates (human/min) of each composition were determined and the results are shown in Table 4. 119564.doc •23- (s > 1343406 Table 4: Copper and Bismuth Removal Rate (A/min) Polishing Composition Additive Copper Removal Rate (A/min) 钽 Removal Rate (A/min) A (Control Base Composition (Batch 1) 2229 208 B (Comparative) Batch 1+400 ppm ΤΑΖ 3337 297 C (Invention) Batch 1+400 ppm TAZ+0.5% by weight CsCl 325 247 D (Comparative) Batch 1+400 ppm BTA 2639 203 E (Invention) Batch 1+400 ppm BTA+0.5% by weight CsCl 218 133 F (Control) Base Composition (Batch 2) 2098 488 G (Invention) Batch 2+ 30 mM CsCl 237 461 Η (Comparative) Batch 2+30 mM Cs2C〇3 2052 530 1 (Invention) Batch 2+30 mM KC1 185 506 The results listed in Table 4 clearly show that it contains chloride anions All of the compositions (Compositions C, E, G, and I) have a 5 to 10 times lower copper removal rate for each vapor-free composition (compositions B, D, F, and F, respectively) The presence of gas anions generally does not affect the rate of ruthenium removal. The presence of other types of anions such as co32_ (composition Η) does not affect the copper removal rate. The data listed in Table 4 also demonstrates Conventional copper inhibitors such as ruthenium and 1,2,4-triazole do not effectively reduce the copper removal rate (comparison of composition Β and D with composition Α). Example 5 This example illustrates the inclusion of an aerosol Effect of gas anion or bromine anion on copper removal rate in polishing compositions of alumina and iodate. Various compositions were evaluated relative to copper removal rate. Each composition contained water, 0.5% by weight of aerosol Alumina and 0.2% by weight of 103, and adjusted to a pH of 2.2 (basic composition) with nitric acid. Various amounts of BTA, potassium 119564.doc -24-1343406 and potassium bromide were added to the base composition. To form three series of compositions. The substrate containing the copper layer was polished with each of the compositions using a Logitech polisher with a soft Politex pad. The Logitech polisher was set to a 10_3 kPa (1.5 psi) orientation. Lower force, platen speed of 110 rpm, carrier speed of 102 rPm, and composition flow rate of 150 ml/min. The copper removal rate (human/πΰη) of each composition was determined and depicted in the diagram of Figure 2. Results. Information listed in Figure 2. Chu seen, base composition (i.e., without addition of BTA, KC1, or adding KBr) exhibit high copper removal rates. The BTA-containing array composition exhibits a high copper removal rate, whereas a series of compositions comprising a gas anion or bromine anion exhibit a reduced copper removal rate. Example 6 This example illustrates the effect of the presence of a gas anion or bromine anion on the copper removal rate in a polishing composition comprising aerosolized ceria and iodate. A variety of compositions were evaluated relative to the copper removal rate. Each composition contained water, 0.5% by weight of fumed cerium oxide and 22% by weight of 艮1〇3, and was adjusted to a pH of 2.2 (basic composition) with nitric acid. Different amounts of BTA, potassium nitrate, gasified If and potassium bromide were added to the base composition to form four series of polishing compositions. A substrate containing a copper layer was polished using a Logitech polisher with a soft Politex pad. The Logitech polisher was set to have a downward force of 10.3 kPa (1.5 psi), a platen speed of 110 rpm, a carrier speed of 1 〇 2 rpm, and a composition flow rate of 15 〇 mi/min. The copper removal rate (in/min) of the master batch was measured and the results are depicted in Figure 5, Figure 564 9564.doc • 25-1343406. It is clear from the information presented in Figure 3 that the base composition (i.e., without the addition of BTA, KN〇3, KC1 or KBr) exhibits a high copper removal rate. Both the ruthenium-containing and KNOB-containing compositions exhibit high copper removal rates, while the inclusion of gas anions or bromine anions exhibits a reduced copper removal rate. Example 7 This example illustrates the effect of the presence of a gas anion or bromine anion on the copper removal rate in a polishing composition comprising aerosolized cerium oxide and hydrogen peroxide. A variety of compositions were evaluated relative to the copper removal rate. Each composition contained water, 0.5% by weight of smoky cerium oxide and 5% by weight of cerium, and was adjusted to a pH of 2.2 (basic composition) with nitric acid. Different amounts of BTA, gasification clock, and bromination clock were added to the base composition to form three series of compositions. A substrate containing a copper layer was polished using a Logitech polisher with a soft Politex pad. The Logitech polisher was set to have a downward force of 10_3 kPa (15 psi), a platen speed of 110 rpm, a carrier speed of 1 〇 2 rpm, and a composition flow rate of 15 〇 ml/min. The copper removal rate (A/min) for each composition was determined and the results are depicted in the graph of Figure 4.

As is clear from the information presented in Figure 4, the base composition (i.e., without the addition of BTA, KCl or KBr) exhibits a high copper removal rate. While the BTA-containing composition exhibits (d) a reduction in rate, the composition comprising a gas anion or a desert anion exhibits a lower copper removal rate. 119564.doc -26 - 1343406 Example 8 This example illustrates the effect of the pH of the polishing composition on the copper removal rate. β Various polishing compositions are evaluated relative to the copper removal rate. Each composition contained water, 0.5% by weight of polycondensed cerium oxide (25 nm in diameter) and 0.2% by weight of potassium iodate, and was adjusted to a value of 1.8, 2.2 or 26 ipH (basic composition) with nitric acid. Different amounts of BTA, potassium bromide, potassium hydride or potassium nitrate were added to the base composition to form four series of compositions. A substrate containing a copper layer was polished using a Logitech polisher with a soft Politex pad. The Logitech polisher was set to have a downward force of 10.3 kPa (1.5 psi), a platen speed of 110 rpm, a carrier speed of 1 〇 2 rpm, and a composition flow rate of 15 〇 mi/min. BTA and salts are added to the base composition by an in-line mixing system built into the Logitech polisher. The copper removal rate (A/min) of each composition was measured, and the results are shown in Table 5. Table 5: Copper removal rate (A/min) Additive pH-1.8 pH: =2.2 pH=2.6 Additive concentration ~~~ 1.32 mM 6.55 mM 1.32 mM 1 6,55 mM 1.32 mM | 6.55 mM No 5907 4388 1552 BTA 4388 7812 5560 5783 2008 2097 KBr 409 269 629 266 384 297 KC1 477 348 356 337 306 170 KNO3 3039 3135 2255 4281 1610 1795 The information presented in Figure 5 shows the presence of gas anions or desert anions at each pH. The copper removal rate is reduced, whereas the composition containing Bta or KNO3 exhibits a high copper removal rate at each pH. The copper removal rate of the base composition itself is strongly dependent on the 1511 value. The base composition 119564.doc -27· 1343406 shows a copper removal rate that drops significantly at pH values greater than 3. In particular, the copper removal rate was 805 person/minute at a pH of 3.04, 219 A/minute at a pH of 3.44, and 168 A/minute at a pH of 3.84. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing the relationship between copper removal rate (A/min) and various compositions at low pH. Figure 2 is a graph of copper removal rate (A/min) versus salt concentration (mM) for various compositions containing alumina and BTA, KCl or KBr at low pH. ® Figure 3 is a plot of copper removal rate (A/min) versus salt concentration (mM) for various compositions containing cerium oxide and BTA, KC1, KBr or KN〇3 at low pH. Figure 4 is a graph of copper removal rate (A/min) versus salt concentration (mM) for various compositions containing cerium oxide and hydrogen peroxide and BTA, KCl or KBr at low pH. 119564.doc 28-

Claims (1)

1343406 Patent Application No. 096110172 1 "^^* I Chinese Patent Application Scope Replacement (January-March) - Patent Application Range: A chemical mechanical polishing system for polishing a substrate comprising: (a) - a polishing assembly comprising a cerium oxide abrasive; (b) a liquid carrier; (0) an oxidizing agent that oxidizes at least a portion of the substrate, wherein the oxidizing agent is a cerium salt and is present in an amount based on the weight of the liquid carrier 5·5 wt% or less; (d) a halogen anion selected from the group consisting of gas, bromine, and combinations thereof, wherein the liquid carrier has a pH of 3 or less; and (e) stupid 2. A polishing system as claimed in claim 2, wherein the liquid carrier comprises water. 3. The polishing system of claim 1, wherein the substrate comprises at least one button layer and at least one copper layer. The polishing system of claim 1, wherein the polishing system comprises a cerium oxide abrasive suspended in the liquid carrier. 5. The polishing system of claim 4, wherein the abrasive is present in an amount of the liquid carrier Calculated from 0.1% by weight to 1% by weight 6. The polishing system of claim 4, wherein the abrasive is present in an amount of 0.5% by weight or less based on the weight of the liquid carrier. 7. The polishing system of claim 1, wherein the polishing component comprises A polishing pad and a cerium oxide abrasive fixed to the polishing pad. 8. The polishing system of claim 1, wherein the oxidizing agent is present in an amount of 0.2% by weight or less based on the weight of the liquid carrier. The polishing system of claim 1, wherein the oxidizing agent is potassium iodate = > 119564-100Q324.doc Γ 343406. The polishing system of claim 1, wherein the halogen anion is selected from the group consisting of: Sources of the group: acid or bromide, alkali metal vapor or bromide, steroid gas or bromide, ammonium or ammonium salt derivative of vapor or bromide, transition metal vapor or bromide and 11. The polishing system of claim 1, wherein the halogen anion is produced by a source selected from the group consisting of hydrogenated gas, magnesium gasification, calcium carbonate, gasification gas, gas Phlegm, Potassium, gasification planer, gasification lithium, gasification sodium, gasification hydrazine, tetrabutylammonium vaporization, tetradecyl vaporized ammonium, tetraethylammonium vapor, tetrapropylammonium vapor, alkylbenzyl Methyl dimethyl vaporized ammonium (wherein the burning base is CVCm burning base), gasification chain, gallium gasification, indium sulfide, gasification hydrazine, zinc hydride, gasified copper, gasified iron, gasified ferrous iron, Tetrabutylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, alkyl benzyl dimethylammonium (which makes the alkyl group Cc 2 decyl) , hydrogen bromide, lithium bromide, potassium bromide, barium bromide 'barium bromide, sodium bromide, magnesium bromide, calcium bromide, barium bromide, barium bromide, aluminum bromide, gallium bromide, indium bromide , cesium bromide, zinc bromide, copper bromide, iron bromide, ferrous bromide and combinations thereof. 12. The polishing system of claim 10, wherein the concentration of the elemental anion is 〇 5 mM to 50 mM. 13. A method of chemical mechanical polishing of a substrate, the method comprising: (i) contacting a substrate with a chemical mechanical polishing system, the chemical mechanical polishing system comprising: (4) a polishing assembly selected from the group consisting of a polishing pad, a group of abrasives I19564-I000324.doc 1343406 and combinations thereof; (b) a liquid carrier; (c) an oxidizing agent that oxidizes at least a portion of the substrate, wherein the oxidizing agent is present in the liquid carrier The weight is 〇, 5% by weight or less; (d) a halogen anion selected from the group consisting of gas, bromine, and combinations thereof, wherein the liquid carrier has a pH of 3 or less; Moving the polishing assembly relative to the substrate; and (ni) grinding at least a portion of the substrate to polish the substrate. 14. The method of claim 13 wherein the liquid carrier comprises water. 15. The method of claim 13 wherein the polishing system comprises an abrasive suspended in the liquid carrier. 16. The method of claim 1, wherein the abrasive is present in an amount of 0.1% by weight based on the weight of the liquid carrier. /. Up to 10 weights 0/〇. 17. The method of claim 15, wherein the abrasive is present in an amount of 〇, 5% by weight or less based on the weight of the liquid carrier. 18. The method of claim 15, wherein the grinding is uniform, (10) the group consisting of: oxidized sulphate, oxidized bromine, sulphur dioxide, oxidized, and combinations thereof, such as 叻 long term 1 3 ' Wherein the polishing system comprises a polishing pad and an abrasive fixed to the polishing pad. The method of claim 13, wherein the oxidizing agent is present in an amount of 0.2% by weight or less based on the weight of the liquid carrier. 21. The method of claim 13, wherein the oxidizing agent is selected from the group consisting of peroxygen gas 1 H9564-l 324.d 〇 ( Γ 343 406 acid decommissioning and combinations thereof. 22. The method of claim 13, wherein The halogen anion is produced by a source selected from the group consisting of acid chloride or bromide, alkali metal vapor or bromide, steroid vapor or ammonium salt of bromide, vapor or bromide or Ammonium salt derivative, transition metal vapor or bromide, and combinations thereof 23. The method of claim 22, wherein the halogen anion is produced by a source selected from the group consisting of: gasification hydrogen, gasification Magnesium, gasified calcium, gasification hydrazine, gasification hydrazine, gasification potassium, gasification planer, gasification lithium, gasification sodium, gasification hydrazine, tetrabutylammonium vaporization, tetradecyl vaporized ammonium, tetraethyl Base gasification ammonium, tetrapropylammonium vaporization, alkylbenzyldifluorenyl ammonium halide (in which alkyl is ruthenium, ^2. alkyl), aluminum chloride 'gallium gallide', indium vaporization, gasification铊, zinc hydride, vaporized copper, ferric chloride, gasified ferrous iron, tetrabutyl bromide, tetrakisole evolutionary money, four B Ammonium bromide, tetrapropylammonium bromide, alkylbenzyl sulfhydryl desertification (wherein the alkyl group is C! - C 2 sulphur), hydrogen bromide, lithium bromide, potassium bromide, bromine planer , cesium bromide, sodium bromide, magnesium bromide, calcium bromide, barium bromide, barium bromide, aluminum bromide, gallium bromide, indium bromide, barium bromide, zinc bromide, copper bromide, bromine The method of claim 22, wherein the concentration of the halogen anion is from 〇5 mM to 50 mM 〇25, such as β, wherein the substrate comprises at least— 26. The method of claim 25, wherein the copper layer is removed from the substrate at a rate of 1 A/min or less. 119564-1000324.doc 1^4J4U6 27. The method of claim 25, wherein the copper layer is removed from the substrate at a rate of 800 A/min or less. 28. The method of claim 25, wherein the copper layer is removed from the substrate at a rate of 500 A/min or less. The method of claim 25, wherein the copper layer is removed from the substrate at a rate of 3 A/min or less. I19564-I000324.doc